Dye forming nitroparaphenylenediamine sulfonyl derivatives

ABSTRACT

Intermediate compounds which can be used to form hair dyes which have the formula:   IN WHICH R1 and R2 are H, alkyl or hydroxyalkyl and may form a heterocyclic ring with the N atom, R3 is H, alkyl or hydroxyalkyl, R4 is H or CH3 and n is 2-6.

United States Patent Kalopissis et a1.

[ DYE FORMING NITROPARAPHENYLENEDIANIINE SULFONYL DERIVATIVES [72] Inventors: Gregoire Kalopissis, Paris; Andree Bugaut,

Boulogne sur Seine, both of France Societe anonyme dite: LOreal, Paris, France [22] Filed: Feb. 9, 1970 [21] AppL No.: 10,040

Related US. Application Data [63] Continuation-impart of Ser. No. 568,118, July 27,

1966, abandoned.

[73] Assignee:

[30] Foreign Application Priority Data July 30, 1965 Luxembourg ..49.214 Jan. 27, 1966 Luxembourg ....50.348 July 4, 1966 Luxembourg ..5l.474

[52] US. Cl ..260/556 AR, 260/293.73, 260/247.1,

260/326 S, 260/573, 260/577, 260/293.79, 260/247.5 R, 260/326 N Primary Examiner-Henry R. Jiles Assistant Examiner S. D. Winters Attorney-Holcombe, Wetherill & Brisebois 51 May 23, 1972 ABSTRACT lntennediate compounds which can be used to form hair dyes which have the formula:

0 0 CH; (III) and H (IV) in which R, and R are H, alkyl or hydroxyalkyl and may form a heterocyclic ring with the N atom, R is H, alkyl or hydroxyalkyl, R is H or CH and n is 2-6.

5 Claims, No Drawings DYE FORMING NITROPARAPHENYLENEDIAMINE SULFONYL DERIVATIVES This application is a Continuation-in-part of application Ser. No. 568,1 18, filed July 27, 1966, now abandoned.

SUMMARY OF THE INVENTION The present invention relates to new intermediate compounds which can be used to form dye compounds which can be used to dye keratin fibers, such as live human hair and animal fibers.

The object of the present invention is to provide improved nitroparaphenylenediamine dye compounds selected from the croup consisting of R1 R-I I(CHz)nN in which R, R and R are selected from the group consisting of H, lower alkyl having one to six carbon atoms and lower hydroxyalkyl having one to six carbon atoms, and R and R are selected from the group consisting of H, lower alkyl having one to six carbon atoms and lower hydroxyalkyl having one to six carbon atoms, and together with the N a group piperidino, morpholino or phtalimido, n is a number from 2 to 6, and the N group is in the 2 or 3 position on the benzene ring, wherein R and R cannot both be H, and the amino group on the benzene ring situated in the ortho position to the nitro group is never tertiary, and when the N0 group is in the 2 position either R or R" must be H, and when R and R are H, R and R are never both ethyl and R" is not methyl, and when the N0 group is in position 3, R must be H and R and R are never both ethyl and R and R are never both H, and

b. the dihydro chloride salts of the compounds of formula (I), and

R-N- (CH2) nC1 (II) in which R, R and R are selected from the group consisting of H, lower alkyl having one to six carbon atoms and lower hydroxyalky] having one to six carbon atoms, and n is a number from 2 to 6 using the intermediate compounds of this invention.

Dyes having formula (I) have the advantage of having, when cold, a great affinity for keratinic fibers. Hair dyes made from these dyes can form very strong shades and the strength of the coloration and the affinity of the dye compound for keratinic fibers, permit the dyes to be used, even in very small quantities, in tinctorial solutions at room temperature. This peculiarity is very valuable because it makes the use of dyes having a relatively poor solubility possible and satisfactory.

It should also be noted that dye colorations of the dyes of the present invention have a particularly good resistance to fading caused by light and washing. Moreover, they may be used in a pH range which is much wider than the presentlyknown range of usage for analogous types of dyes. They may in fact be used in compositions having a pH of 4 to 10. The preferable range is 6-10.

Dyes of the present invention also have the peculiarity of having as a substituent on one of the amino groups fixed on the benzene ring, a chain which has a terminal amino group which is quatemizable when said terminal amino group is tertiary. The quaternary compounds thus obtained may also be used as hair dyes in the same way as the corresponding tertiary compounds, and the chloro compounds of formula ll.

The tinctorial compositions of this invention do not require the addition of peroxides such as hydrogen peroxide as other hair dyes do in order to develop the color. However, other ingredients commonly used in hair-dyeing treatments may be added to these tinctorial compositions, such as organic solvents, thickeners, detergents, lacs, etc.

With dyes of the type conforming to the invention, it is possible to notably vary the dye compound concentration in the tinctorial solutions, but the preferable concentration is between 0.1 and 3.5 percent.

The time during which the aforementioned tinctorial solutions are in contact with the hair may vary within wide limits, but preferably it should be between 5 and 30 minutes. The temperature at which the tinctorial solutions are applied may also be varied, but in most cases they may be advantageously used at ordinary room temperature.

Any of the dyes of this invention may be mixed with other dyes of the invention or with any other nitrated dyes, such as, nitroorthophenylenediamine, nitroparaphenylenediamine and alkyl or hydroxyalkyl derivatives of these compounds. The new dyes of the invention may also be mixed with azo or anthraquinone dyes or other types of dyes usually used for hair-dyeing.

The intermediate dye forming compounds of this invention are compounds which have the formula:

(:0 CH3 (III) in which R and R are selected from the group consisting of hydrogen, lower alkyl and lower hydroxyalkyl, and may form a heterocyclic ring with the nitrogen atom to which they are attached, R is selected from the group consisting of hydrogen, lower alkyl and lower hydroxyalkyl, R is selected from the group consisting of hydrogen, and methyl, and n is an integer between 2 and 6 inclusive, and a compound having the formu- SOQ-Rr N/ (CH1) n N in which R,, R R R and n have the meaning defined above, in which said lower alkyl and hydroxyalkyl groups have one to six carbon atoms.

Illustrative methods of preparing the dyes of the invention and examples of how to use the aforesaid dyes are set forth below.

EXAMPLE 1 Preparation of 1-N-methylamino-2-nitro-4-N-( ,8- diethylamino )ethylamino benzene First step: Preparation of 1-N-methylai'nino-2-nitro-4-[N'-(B- diethylamino)ethyl-N'-benzenesulfonyl]amino benzene.

0.575 mols of diethylaminoethylchloride hydrochloride in solution in 150 cm of water and 150 cm of 2 N sodium hydroxyde is added little by little, at about 80 C, to a solution of 0.326 mols (100 g) of l-methy1amino-2-nitro-4-N'- benzenesulfonylamino benzene in 350 cm of normal sodium hydroxyde. The reaction mixture is held at 80 C for three hours. After cooling, drying yields 130 g of l-N-methylamino- 2-nitro-4-[ N B-diethylamino )ethyl-N-benzenesulfonyl]amino benzene. The crude product is washed in normal sodium hydroxyde and then with water, to eliminate any trace of the starting product. After recrystallization in alcohol, the end product melts at 1 12 C.

Second step Preparation of l-N-methylamino-2-nitro-4-[N- (B-diethylamino)ethyl]amino benzene dihydrochloride.

0.148 mols (60 g) of l-N-methylamino-2-nitro-4-N- benzenesulfonyl-N-/3(diethylamino)-ethylamino benzene is added little by little, while stirring, to 200 cm of concentrated sulfuric acid, while keeping the temperature at C. The reaction mixture is left for 6 hours at this temperature, and then poured over 1.5 kg of cracked ice. After alkalizing the product with 10 N sodium hydroxyde, it is extracted with ethyl acetate. The ethyl acetate solution is washed with water, dried on sodium sulfate, and filtered.

The cooled ethyl acetate solution is saturated with gaseous hydrochloric acid and drying yields 48 g of the dihydrochloride of l -N-methylamino-2-nitro-4-N'-B- (diethylamino )ethylamino benzene.

The base is then isolated from this dihydrochloride in a conventional manner.

EXAMPLE 2 Preparation of 1-N-B-diethylaminoethyl-amino-2-nitro-4-N'- methylamino benzene.

First step: Preparation of l-N-benzenesulfonylamino-2-nitro-4 -(N'-methyl-N-acetyl)-amin0 benzene.

Analysis: Calculated for Found rs i= a Second step: Preparation of 1-(N-benzene-sulfonyl-NB- diethyl-arninoethyl )-amino-2-nitro-4-( N-methyl-N '-acety 1} amino benzene 0.152 mol (26 g) of hydrochloride of diethylaminoethylchloride in solution in cm of water and 100 cm of 2 N sodium hydroxide are simultaneously added little by little to a solution of 0.05 mol (17.4 g) of l-N-benzenesulfonyl-amino- 2-nitro-4-(N'-methyl-N-acetyl)-amino benzene in 60 cm of normal sodium hydroxide at about 60 C. The addition finished, the reaction mixture is kept at 60 C for 3 hours. After chilling, it is extracted with ethyl acetate and the ethyl acetate solution is washed first with normal sodium hydroxide, and then with water to eliminate the initial product in the form of its tosylate. The product is then extracted using iced normal hydrochloric acid, in the form of its hydrochloride. Alkalization of this hydrochloric solution using normal sodium hydroxide leads to the precipitation of 9 g of l-( N-benzenesulfonyl- N-B-diethylaminoethyl )-amino-2-nitro-4-( N -methyl-N acetyl)-amino benzene which, after recrystallization in a mixture of toluene and hexane, melts at C. lts analysis is:

Analysis: Calculated for Found C 56.25 56.43-56.23 H 6.25 6.29-6.15 N 12.50 12.67-12.68

Third step: 0.0133 mol(6 g) of l-[N-benzenesulfonyl-N-,B- diethyl-aminoethyl ]amino-2-nitro-4-( N '-methyl-N-acetyl amino benzene in 50 cm of concentrated hydrochloric acid is heated to reflux for 2 hours. After dilution, it is chilled while adding 5 N sodium hydroxide. Drying yields 3.2 g of l-N-B- diethyl-aminoethylamino-Z-nitro-4-methylamino benzene which after recrystallization in a mixture of benzene and hexane, melts at 74 C.

The analysis of this product is:

nitro-4-amino benzene First step: Preparation of 1-N-p-toluene-sulfonylamino-2- nitro-4-acetylarnino benzene This product is prepared in the usual manner, by reacting ptoluene sulfochloride with 1-amino-2-nitro-4-acetyl-amino benzene in solution in pyridine.

After recrystallization in alcohol, this product melts at 161.5 C and its analysis yield the following results:

Calculated for Analysis: Found is ia a s C 51.57 51.51-51.77 H 4.29 4.42-4.12 N 12.03 12.11-12.12

Second step: Preparation of 1-N-p-toluenesulfonyl-N-fldiethyl-aminoethyl-amino-2-nitro-4-acety1amino benzene 0.086 mols (14.8 g) of B-diethylarnino-ethylchloride hydrochloride in solution in 50 cm of water, and 60 cm of 2 N sodium hydroxide, are simultaneously added little by little, at about 60 C, to a solution of 0.0286 mols g) of l-N-ptoluene-sulfonyl-amino-2-nitro-4-acetylamino benzene in 40 cm of normal sodium hydroxide. When this addition has been completed, the reaction mixture is kept for three hours at 60 C. After cooling, it is extracted with ethyl acetate, and the resulting ethyl acetate solution washed first with sodium hydroxide and then with water in order to eliminate the starting product in the form of the tosylate. The product is then extracted in the form of its hydrochloride, using iced normal hydrochloric acid. The resulting solution is alkalized with sodium hydroxide and 7 g of 1-(N-p-toluenesulfonyl-N-B- diethylaminoethyl)-amino-2-nitro-4-acetylamino benzene is precipitated. When dried under vacuum and recrystallized in a toluene-hexane mixture, this melts at 166 C.

The analysis of this product yields the following results:

Analysis: Calculated for Found C ,H O,N S

C 56.25 56.13-56.30 H 6.25 6.29-6.32 N 12.50 12.40-12.45

Third step: Preparation of l-N-B-(diethylarnino)-ethylamino- 2-nitro-4-acetylamino benzene The analysis of this product is:

Analysis: Calculated for Found CIIHZOSNQ C 57.14 57.34-57.40 H 7.48 7.45-7.52 N 19.04 19.24-19.20

Fourth step: 0.02 mol (5.9 g) of l-N-B-(diethylamino)- ethylamino-Z-nitro-4-acetylamino benzene is dissolved in 30 cm of 5 N hydrochloric acid, then heated for 1 hour to reflux. After chilling it is alkalized and, on drying, yields 5 g of l-N-B- (diethylamino)-ethylamino-2-nitro-4-amino benzene which, after recrystallization in a mixture of benzene and hexane, melts at 65-66 C.

EXAMPLE 4 Preparation of dihydrochloride of 1-N-methy1amino-2-nitro-4 -N'-m-aminobuty1amino benzene The reactions utilized to prepare this product may be schematically represented in the following manner:

@spyomn-mr.

NO: O:

NHCH; NHCH:

First step: Preparation of l-N-methy1amino-2-nitro-4-(N'-' Analysis: Calculated for Found C,,H N,O S Br C 46.15 46.30-46.24 H 4.52 4.59-4.41 N 9.50 9.53-9.77

on the other hand, 30 g of bis-[N'-( 4-methylamino-3-nitro)- phenyl]-benzenesulfamidobutane which melts at 245 C and of which the analysis is:

Analysis: Calculated for Found ao az s s z Second step: Preparation of l-N-methylamino-2-nitro-4-(N- benzenesulfonyl-N'-phthalimidobutyl )-amino benzene 0.25 mol (110.5 g) of 1-N-methylamino-2-nitro-4-(N- Analysis: Calculated for Found CMHMNGOOS C 59.05 59.16-58.99 H 4.72 4.89-4.90 N 11.02 10.99-11.09

Third step: Preparation of 1-N-methylamino-2-nitro-4-( N'- benzenesulfonyl-N'-tu-aminobutyl )-amino benzene.

0.04 mol of hydrazine hydrate is added to a solution of 0.02 mol (10.16 g) of substituted phthalimide in 80 cm of propanol, and then heated for 30 minutes in a boiling waterbath. Most of the resultant phthalhydrazide is eliminated by filtration of the hot reaction mixture. After cooling, an orange oil is isolated by decantation and dissolved in ethyl acetate. This ethyl acetate solution is extracted with a /2 N hydrochloric solution. The aqueous hydrochloric phase is alkalized, and drying yields 4.5 g of 1-N-methylamino-2-nitro-4-(N'- benzenesulfonyl-N'w-aminobutyl)-amino benzene which, after recrystallization in ethyl acetate, melts at 135 C. The analysis of this product is:

Analysis: Calculated for Found C 53.96 54.11-53.95 l-l 5.82 5.76-5.91 N 14.82 14.93-14.80

Analysis: Calculated for Found C X: 42.44 42.49-42.38 H 6.43 6.41-6.25 N 18.00 18.05-18.10

EXAMPLE 5 Preparation of dihydrochloride of l-N-methylamino-2-nitro-4 -N'--y-[ N B-hydroxyethyhrnethyl l-y-arninopropyl-amino benzene The reactions utilized to prepare this product may be schematically represented in the following manner:

@- s 02 carom-0mm N CH;

CHz-CHzOH a NHCH:

N CHrCHz-OH NO; HCl

N0 ZHCl NHCH:

First step: Preparation of l-N-methylamino-2-nitro-4-(N'- benzenesulfonyl-N'--y-[N' B-hydroxyethyl-methy] aminopropyl )-amino benzene.

0.0466 mol (20 g) of l-N-methylamino-2-nitro-4-(N- benzenesulfonyl-N-'y-bromopropyl)-amino benzene is heated in 0.373 mol (28 g) of methyl-B-hydroxyethylamine for 7 hours at C. The excess methyl-B-hydroxyethylamine is driven off under vacuum. The residue is recovered in iced 2 N hydrochloric acid. Drying then yields the desired product in the form of the hydrochloride. This hydrochloride is dissolved in hot water and rendered alkaline by means of a sodium hydroxide solution. After cooling, drying yields 16 g of l-N- methylamino-2-nitro-4-( N-benzenesulfonyl-N -'y- N [3- hydroxyethyl-methyl ]--y-amin opropyl )-amino benzene which, after recrystallization in methanol, melts at 85 C. The analysis of this product is:

Second step: Preparation of the dihydrochloride of l-N- methylamino-2-nitro-4-( N -'y-[ N B-hydroxyethyl-methyl 'y-aminopropyl )-amino benzene.

0.048 mol (2.04 g) of l-N-methylamino-2-nitro-N'- benzenesulfonyl-4-( N'-'y-[ N '-(fl-hydroxyethyl-methyl 1-yamino-propyl)-amino benzene is heated to reflux for 2 hours in 6 cm of concentrated hydrochloric acid. After dilution, it is alkalized with sodium hydroxide and the resulting solution is extracted using methylisobutylcetone. After the methylisobutylcetone has been driven off under vacuum, the oily residue is redissolved in normal propyl alcohol. The well-cooled alcoholic solution is saturated with dry gaseous hydrochloric acid. Drying yields l.4 g of the dihydrochloride of l-N- methylamino-2-nitro-4-(N '-'y[N' B-hydroxy-ethyl-methyl 'y-arninopropyD-amino benzene, which melts with decomposition at C. The analysis of this product is:

Preparation of the dihydrochloride of l-N-B-ethylamino-Z- nitro-4-arnino benzene The reactions utilized to prepare this product may be schematically represented in the following manner:

NHC CH E SOK a -C a phthalimidoethyl )-amino-2-nitro-4-N-acetylamino benzene.

0.01 mol (4.56 g) of 1-(N-p-toluenesulfonyl-N-B-bromoethyl)-amino2-nitro-4-N'-acety1amin0 benzene is dissolved in 16 cm of dimethylformamide. 0.012 mol of potassium phthalimide is added and the reaction mixture is heated for 1 hour in a boiling water-bath. While hot, it is filtered and poured into 200 cm of water. Drying yields g of a crude product which, after recrystallization in a acetone-water mixture, melts at 205 C. The analysis of this product is:

Analysis: Calculated for Found C H O PLS Second step: Preparation of 1-( N-p-toluenesulfonyl-N-B- amino-ethyl)-amino-2-nitro-4-N'-acetylamino benzene.

0.215 mol (112.2 g) of l-(N-p-toluenesulfonyl-N-fiphthalimidoethyl )-amino-2-nitro-4-N-acetylamino benzene is dissolved in 600 cm of propanol. 0.43 mol (22 g) ofhydrazine hydrate is added to this solution and it is heated for 20 minutes in a boiling water-bath. By filtration of the hot reaction mixture, 34 g of phthalhydrazide is isolated. The propanolic mother liquor is chilled at 5 C. A red oil separates out and is eliminated through decantation. Then the alcoholic solution is saturated with dry gaseous hydrochloric acid. Drying yields the desired product in the form of the hydrochloride. The base is liberated in the customary manner. 66 g of l-(N-ptoluenesulfonyl-N-B-amino-ethyl)-arnino-2-nitro-4-N'- acetylamino benzene is thus obtained which, after recrystallization in pyridine, melts at 223 C. The analysis of this product is:

Analysis: Calculated for Found The oil eliminated in the course of the preparation crystal- 10 lizes easily in methanol. This secondary product (F=l75) is l -[N-B-(p-toluenesu1fony1)-aminoethyl]-amino-2-nitro-4-N'- acetylamino-benzene.

Third step: Preparation of dihydrochloride of l-N-B- aminoethylamino-2-nitro-4-amino benzene.

0.102 mol (40 g) of 1-(N-p-toluenesulfonyl-N-B-aminoethyl)-amino-2-nitro-4-N'-acetylamino benzene is heated with 200 cm of 7 N hydrochloric acid in a boiling water-bath for 1 hour. After chilling, drying yields 26.7 g of the dihydrochloride of 1-N-B-aminoethylamino-2-nitro-4-amino benzene which, after recrystallization in concentrated hydrochloric acid, yields the following results when analyzed:

Analysis: Calculated for Found C 35.69 35.50-35.60 H 5.20 5.01-5.10 N 20.82 21.00-20.82

EXAMPLE 7 Preparation of the dihydrochloride of 1-N-methy1amino-2- nitro-4-N'-w-aminohexylamino benzene The reactions utilized to prepare this product may be schematically represented in the following manner:

Br(CH2)oBr p NHCH;

0 1 @902 cam-Br Q: /NK

NHCHa O .0 l @s 02 (Cam-N C g NHr-NHzHzO NHCH;

B 0 CHM-NH H CH2) NH2 2 i N01 NOz-ZHOl NHCH; NHCH:

Analysis: Calculated for Found C H N Br SO,

C 48.51 48.52-48.30 H 5.10 5.32-5.26 N 8.93 9.18-9.20

on the other hand, 4 g of bis-N-[4-N-methylamino-3-nitrophenyl]-benzenesulfamidohexane, which melts at 200 C. Analysis thereof yields the following results:

Analysis: Calculated for Found C E-I N S O C 55.17 55.33-55.12 H% 5.17 5.13-5.12 N 12.06 12.17-12.01

Second step: Preparation of l-N-methylamino2-nitro-4-(N'- benzenesulfonyl-N-w-phthalimidohexyl)amino benzene.

0.0268 rnol (12.6 g) of 1-N-methylamino-2-nitro-4-(N- benzenesulfonyl-N'-w-bromohexyl)-amino benzene is dissolved in 50 cm of dimethylformamidc. 0.0322 rnol (5.96 g) of potassium phthalimide is added and the reaction mixture is heated for an hour in a boiling water-bath. It is poured into 400 cm of water and drying yields 13.8 g of a crude product which, after recrystallization in ethyl acetate, melts at 149 C.

Analysis of the end product yields the following results:

Analysis: Calculated for Found C,,H ,,N,SO,,

Third step: Preparation of 1-N-methylamino-2-nitro-4-(N'- benzenesulfonyl-N '-w-aminohexyl)-arnino benzene.

2 g of hydrazine hydrate are added to a solution of 0.0193 mol (10.37 g) of substituted phthalimide in 80 cm of propanol. Then it is heated for 30 minutes in a boiling waterbath. The major portion of the resultant phthalhydrazine is eliminated by filtration of the hot reaction mixture.

After chilling, an orange oil is isolated by decantation and placed in solution in ethyl acetate. This solution of ethyl acetate is extracted using :6 N hydrochloric acid.

After the hydrochloric phase has been alkalized with sodium hydroxide, drying yields 3.5 g of l-N-methylamino-Z- nitro-4-(N-benzenesulfonyl-N'w-aminohexyl)-amino benzene which melts at 130 C.

The propanolic mother liquor, after saturation with dry hydrochloric acid, yields another 2 g of the desired product, isolated in the form of the hydrochloride.

Fourth step: Preparation of the dihydrochloride of l-N- methylamino-2-nitro-4-( Nw-aminohexyl )-amino benzene.

0.008 mol (3.2 g) of 1-N-methylamino-2-nitro-4-(N'-maminohexyl)-amino benzene is heated in solution in 10 cm of concentrated hydrochloric acid for 30 minutes in a boiling water-bath. After cooling and addition of 10 cm of absolute alcohol, drying yields 2 g of dihydrochloride of l-N- methylamino-2-nitro-4-(N'-m-aminohexyl)-amino benzene. After recrystallization in concentrated hydrochloric acid mixed with an equal volume of alcohol, analysis of the product yields the following results:

Analysis: Calculated for Found C 46.01 46.30-46.23 H 7.08 7.30-7.27 N 16.52 16.51-16.50

EXAMPLE 8 First process for preparation of 1-N-methylamino-2-nitro-4- N'-B-aminoethylamino benzene The reactions utilized to prepare this product may be schematically represented in the following manner:

Analysis: Calculated for Found C 57.53 57.28-57.10 l-l 4.17 3.98-4.20 N 11.66 11.67-11.66

Method (b): 0.05 mol (17.25 g) of the potassium salt of l- N-methylamino-2-nitro-4-N'-benzenesulfonyl-amino benzene is dissolved in 50 cm of dimethylformamide. 13.97 g of B- bromoethyl-phthalimide is added and the mixture is heated for 1 hour at 140 C. After chilling, the reaction mixture is poured into a liter of water and drying yields a gummy product which, after three crystallizations in toluene, yields 12 g of l-N- methylamino-2-nitro-4-(N-benzenesulfonyl-N'-B- phthalimidoethyl)-amino benzene, which melts at 218 C.

The yield is poorer than that obtained by the preceding method.

Second step: Preparation of l-N-methylamino-2-nitro-4-(N- benzenesulfonyl-N'-/3-aminoethyl )-amino benzene.

0.119 mol (57 g) of 1-N-methylamino-2-nitro-4-(N'- benzenesulfonyl-N'-,B-phthalimidoethyl)-amino benzene is dissolved in 350 cm of propanol. 0.238 mol (11.9 g) of hydrazine hydrate is added to this solution and heated for an hour in a boiling water-bath. After cooling the reaction mixture at the ambient temperature, the resulting phthalhydrazide is eliminated by filtration.

The propanolic solution is then concentrated to about 80 cm After chilling, 30 g of the desired product are obtained in the form of an oil which crystallizes slowly. After recrystallization in a mixture of ethanol and water, the product melts at 1 C. Analysis yields the following results:

Analysis: Calculated for Found C 51.43 51.41-51.37 H 5.14 5.19-5.28 N 16.00 16.01-16.02

Analysis: Calculated for Found C% 51.42 51.13-51.22 H 6.66 6.51-6.51 N 26.66 26.81-26.59

EXAMPLE 9 Preparation of the dihydrochloride of 1-N-B-(diethylamino)- ethylamino-2-nitro-4-N'-di-B-hydroxyethylamino benzene The reactions utilized to prepare this product may be schematically represented in the following manner:

First step: Preparation of N-benzene-sulfonyl-l-N-B-(diethylamino )-ethylamino-2-nitro-4-acetamido benzene.

The sodium salt of l-N-benzene-sulfonyl-amino-2-nitro-4- acetamido benzene is used as raw material. This salt may be prepared in the manner indicated in Luxembourg Pat. application No. 49,213 filed 30 July 1965. It should be noted, however, that in this Luxembourg patent it is indicated that the reaction may be carried out in water. It has since been found that the yield is much higher if dimethyl-formamide is used as the solvent, and dimethyl-formamide has accordingly been used in the first step of the present example, which will now be described. 0.2 mol (71.4 g) of 1-N-benzene-sulfonyl-amlno-Z- nitro-4-acetamino benzene is dissolved in 280 cm of dimethyl-formamide at C. 0.2 mol (27.1 g) of diethylarnino-ethyl chloride is quickly added and the reaction mixture is heated for 20 minutes in a boiling water-bath. It is cooled, then poured into a liter of water and, on drying, yields 70 g of a crude product which, after being treated with a 2 N sodium hydroxide solution to eliminate a little of the initial product, washing with water and recrystallization in alcohol, melts at C.

Second step: Preparation of the dihydrobromide of l-N- B- (diethylamino)-ethylamino2-nitro4-amino benzene.

0.217 mol of N-benzene-sulfonyl-l-N-B-(diethylamino)- ethylamino-2-nitro-4-acetamido benzene in 200 cm of hydrobromic acid at a density d=1.78 is added to cm of water and heated for 4 hours in a boiling water-bath. After cooling, drying yields 72 g of the dihydrobromide. The base obtained from this dihydrobromide melts at 65 C. Third step: Preparation of dihydrochloride of (diethylamino)-ethylamino-2-nitro-4-N-di-B-hydroxyethylamino benzene.

0.05 mol (20.7 g) of dihydrobromide of l-N-B-(diethylamino) ethy1amino-2-nitro-4-amino benzene is heated for 2 hours in a boiling water-bath with 25 cm of 99.5% glycol bromohydrin (0.2 mol) with 5 cm of water and g of calcium carbonate.

200 cm of water are added, the mixture is filtered and alkalized with sodium hydroxide and the sodium solution is extracted, using methyl-isobutyl-cetone. After the solvent has been driven off under vacuum, the oily residue is redissolved in 100 cm of absolute alcohol and this alcohol solution is cooled and saturated with dry gaseous hydrochloric acid. Drying yields 17 g of the dihydrochloride of l-N-fi- (diethylamino )-ethylamino-2-nitro-4-N'-di-,B-hydroxyethylamino benzene which, after recrystallization in 20 cm of absolute alcohol with 3 cm of concentrated hydrochloric acid, melts with decomposition between 140 and 145 C. The analysis of the end product is:

Preparation of l-N-7-(diethylamino)propylamino-2-nitro-4- N '-di-B-hydroxyethylamino benzene dihydrochloride.

The reactions utilized in the course of preparation may be schematically illustrated as follows:

CH -CO H CzHs Glycol hydrobromide is condensed on l-N-y (diethylamino) propylamino-2-nitro-4-amino benzene dihydrochloride in the presence of calcium carbonate. This dihydrochloride is obtained by condensing diethylaminopropyl-chloride in dimethyl-formamide on the sodium salt of 1-N-benzenesulfonyl-2-nitro-4-acetamido benzene, in the manner described in Luxembourg application Ser. No. 49213 filed July 30, 1965, and by said hydrolysis of the l-N-benzene-sulfonyl-N--y-( diethylamino )propylamino-2- nitro-4-acetamido benzene thus obtained.

First step: Preparation of l-N-benzenesulfonyl-N-y- (diethylamino )-propylamino-2-nitro-4-acetamido benzene.

0.6 mols (215 g) of the sodium salt of l-N-benzenesulfonylamino-2-nitro-4-acetamido benzene is dissolved in 860 cm3 of dimethylformamide at C. 0.62 mols (93 g) of diethylamino-propylchloride is added fairly rapidly and the reaction mixture heated for an hour in a boiling water-bath. It is then cooled and poured into 4 liters of ice water. Drying yields the crude product, which is treated with a normal sodium hydroxide solution to eliminate a little of the initial product, washed with water, dried, and recrystallized in methanol. The yield is 163 g of the crystallized product, which melts at 98 C.

Second step Preparation of l-N-y-( diethy1amino)- propylamino-2-nitro-4-amino benzene dihydrochloride.

0.138 (61.6 g) of the sulfonamide previously obtained is heated for four hours at 80 C in 165 cm3 of concentrated sulfuric acid. The reaction mixture is poured over ice, alkalized with a sodium hydroxide solution and the hydrolyzed product is extracted, using ethyl acetate. The ethyl acetate is driven off under vacuum and the oily residue dissolved in 100 cm of methanol. This methanolic solution is saturated with dry gaseous hydrochloric acid and drying yields 38.2 g of l-N-y- (diethylamino)-propy1amino-2-nitro-4 amino benzene dihydrochloride, which melts and decomposes at 190 C. Third step: Preparation of 1-N--y-(diethy1amino)- propylamino-2-nitro-4-N'-di-Bhydroxyethylamino benzene dihydrochloride.

0.1 mols (34 g) of l-N-'y-(diethylamino)-propylamino-2- nitro-4 amino benzene is heated for 2 hours in a boiling waterbath, with 50 g (0.4 mols) of 99.5% glycol bromohydrin added to 10 cm of water and 20 g of calcium carbonate. 200 cm of water is then added, and the solution filtered. After alkalization with sodium hydroxide, the solution is extracted with butyl-alcohol. The solvent is eliminated under vacuum and the oily residue dissolved in methanol. The methanolic solution is saturated with dry gaseous hydrochloric acid and drying yields 30.12 g of the dihydrochloride, which melts and decomposes at C.

The dyes that are made with the intermediate compounds of this invention are used in the customary manner which is illustrated by the following Examples.

EXAMPLE 11 The following solution is prepared:

iodide of fi-[N-methyl-N( 3-nitro-4-N'- methylamino )phenyi ]arninoethyl methylpiperidinium 4 g Lauric alcohol oxyethylenated with 10.5

molecules of ethylene oxide 5 g Sodium carbonate, q.s.p. pH 9 Water, q.s.p. 100 cm This solution, applied to deep blond hair and left for 15 minutes, yields, after rinsing and shampooing, a strong aubum.

EXAMPLE 12 The following solution is prepared:

Dihydrochloride of l-N-methylamino-Z-nitro- 4-N'-methyl-N'-B-( methylhydroxyethylamino)ethylamino benzene 0.17 g l-N--y-(diethylaminopropyl)amino-2-amino-4- nitrobenzene 0.5 g Lauric alcohol oxyethylenated with 10.5

molecules of ethylene oxide g Sodium carbonate, q.s.p. pH 9 Water, q.s.p. 100 cm This solution, applied for 15 minutes to 100% white hair, yields, after rinsing and shampooing, a reddish-gold blond.

EXAMPLE 13 The following solution is prepared:

l-N-methylamino-2-nitro-4-N -m ethyl-N'-B- piperidino-ethylamino benzene 0.01 g Laurie alcohol oxyethylenated with 10.6

molecules of ethylene oxide 5 g Monoethanolamine, q.s.p. pH 9 Water, q.s.p. 100 cm This solution, applied for 5 to 10 minutes to hair bleached platinum, yields, after rinsing and shampooing, a rosewood shade.

EXAMPLE 14 The following solution is prepared:

Dihydrochloride of l-N-methylamino-2-nitro- 4-N '-methyl-N'-diethylamino-ethylaminobenzene 0.03 g 1-N-'y-(diethylaminopropyl)-amino-2-amino-4- nitro benzene 0.01 g Laurie alcohol oxyethylenated with 10.5

molecules of ethylene oxide 5 g Monoethanolamine, q.s.p. pH 9 Water,q.s.p. 100 cm This solution, applied for 10 to 15 minutes to hair previously bleached platinum, yields, after rinsing and shampooing, a light copper mahogany tint.

EXAMPLE 15 The following solution is prepared:

l-N-/3-piperidinoethylamino-2-nitro-4-N'- methylamino-benzene 0.084 g l-N-7-( diethylaminopropyl )-amino-2-amino-4- nitro benzene 0.035 g Laurie alcohol oxyethylenated with 10.5

molecules of ethylene oxide 5 g Water, q.s.p. 100 cm This solution, applied to 100% white hair for 15 minutes, yields, after rinsing and shampooing, a reddish blond.

EXAMPLE 16 The following solution is prepared:

diethylaminoethyl lamino-benzene 0.152 g 4-nitro-l,3-phenylenediamine 0.030 g Laurie alcohol oxyethylenated with 10.5

molecules of ethylene oxide 5 g Sodium carbonate 2 N, q.s.p. pH 9 Water, q.s.p. cm

This solution applied to 100% white hair for 15 minutes, yields, after rinsing and shampooing, a beige shade.

EXAMPLE 17 The following solution is prepared:

l-N-fi-piperidinoethylamino-2-nitro-4-aminobenzene 0.235 g Laurie alcohol oxyethylenated with 10.5

molecules of ethylene oxide 5 g Water, q.s.p. 100 cm This solution applied to light chestnut hair for 10 minutes, yields, after rinsing and shampooing, a strong violine chestnut.

EXAMPLE 18 The following solution is prepared:

Dihydrochloride of l-N-methylamino-Z-nitro- 4-N'-(/3-diethylamino)-ethylamino-benzene 0.5 g l-N-methylamino-2-nitro-4-N '-[3-piperidinoethylamino benzene 0.2 g Lauric alcohol oxyethylenated with 10 molecules of ethylene oxide 5 g Monoethanolamine, q.s.p. pH 9 Water, q.s.p. 100 cm This solution, applied to light chestnut hair for 10 to 15 minutes, yields, after rinsing and shampooing a light chestnut with watery rose glints.

EXAMPLE 19 The following solution is prepared:

lodide offi [N-methyl-N-(3-nitro-4-N'- methylamino)phcnyl l-aminoethylmethylpipen'dinium 0.4 g Dihydrochloride of l-N-methylamino-Z-nitrm 4-N'-(B-diethylamino)ethylamino benzene 0.2 g Dihydrochloride of l-N-methylamino-Z-nitrohydroxyethylamino)-ethylamino benzene 0.15 g Laurie alcohol oxyethylenated with 10.5

molecules of ethylene oxide 5 g 2 N Sodium carbonate, q.s.p. pH 8.5 Water, q.s.p. 100 cm This solution, applied to deep chestnut hair for 20 minutes, yields, after rising and shampooing, a deep violine chestnut.

EXAMPLE 20 The following solution is prepared:

l-N-[3-piperidinoethylamino2-nitro-4-amino This solution, applied to deep chestnut hair for 20 to 25 minutes, yields, after rinsing and shampooing, a deep chestnut with violet glints.

EXAMPLE 21 The following solution is prepared:

Dihydroehloride of l-N-methylamino-Z-nitro- 4-( N -methyl-N' -B-aminoethyl )-amino benzene 0.03 g 4-nitro-l,3-phenylenediamine 0.05 g Laurie alcohol oxyethylenated with 10.5

molecules of ethylene oxide 7 g Sodium carbonate, q.s.p. pH 7 10 Water, q.s.p. 100 cm This solution, applied to 100% white hair for minutes, yields, after rinsing and shampooing, a beige tint.

EXAMPLE 22 15 The following solution is prepared:

l-N-,B-(methyl-hydroxyethyl aminoethylamino-Z-nitro-4-N "methylamino 2Q benzene 0. 14 g N--y-(diethylaminopropyl)amino-2-amino-4- nitro benzene 0.05 g Laurie alcohol oxyethylenated with 10 molecules of ethylene oxide 5 g Sodium carbonate, q.s.p. pH9 25 Water, q.s.p.

This solution applied to 100% white hair for 15 minutes yields, after rinsing and shampooing, a reddish blond.

EXAMPLE 23 The following solution is prepared:

lodide of fi[N-( 2-nitro-4-N-methylamino)- phenyl]-aminoethyl-methylpiperidinium 0.21 g l-N-'y-( diethylaminopropyl )-amino-2-amino-4- nitro-benzene 0.05 g Lauric alcohol oxyethylenated with 10.5

molecules of ethylene oxide 5 g Monoethanolamine, q.s.p pH 7 40 Water, q.s.p. l00 cm This solution, applied to 100% white hair for 15 minutes, yields, after rinsing and shampooing, a light copper mahogany.

EXAMPLE 24 The following solution is prepared:

lodide of B[N-( 2-nitro-4-amino)-phenyl]- aminoethyLmethylpiperidinium 0.28 g Laurie alcohol oxyethylenated with 10.5

molecules of ethylene oxide 2 g Sodium carbonate, q.s.p. pH 9 Water, q.s.p. l00 cm This solution, applied to light chestnut hair for 10 minutes, yields, after rinsing and shampooing, a strong auburn.

EXAMPLE 25 The following solution is prepared:

Dihydrochloride of l-N-methylamino-Z-nitro- 4-(N'-methyl-N'-fi-aminoethyl)-amino This solution applied to light chestnut hair for 10 minutes, yields, after rinsing and shampooing, a deep violine mahogany. 7

EXAMPLE 26 The following solution is prepared:

Dihydrochloride of l-N-B-aminoethylamino-Z- nitro-4-N-bis-B-hydroxyethylamino benzene 0.36 g Laurie alcohol oxyethylenated with 10.5

molecules of ethylene oxide 5 g Sodium carbonate, q.s.p. pH 7 Water, q.s.p. cm

This solution, applied to 100% white hair for 15 minutes, yields, after rinsing and shampooing, a violet blue.

EXAMPLE 27 The following tinctorial composition is prepared:

[ 1-N-methylarnino-2-nitro-4-N'-fiaminoethylamino-benzene1- monohydrobromide 0.73 g Lauric alcohol oxyethylenated with 10.5 moles of ethylene oxide 5 g Na C0 in 2 N solution, q.s.p. pH 8 Water, q.s.p. 100 g This composition is applied to natural light chestnut hair and left for 10 minutes, followed by rinsing and shampooin g.

The result is a deep violine hue.

EXAMPLE 28 The following tinctorial composition is prepared:

[ l -N-B-hydroxy-ethylamino-2 -nitro-4-N -3- diethylaminoethylamino-benzene dihydrochloride 0.296 g 1-N-B-aminoethylamino-Z-nitro-4-methyl-5- amino-benzene 0.042 g Laurie alcohol oxyethylenated with 10.5 mols of ethylene oxide 2 g Na CO in twice normal solution, q.s.p. pH 9 Water, q.s.p. 100 g This composition is applied to natural 100% white hair and left for 10 minutes, followed by rinsing and shampooing.

The result is a reddish blond.

EXAMPLE 29 The following tinctorial composition is prepared:

[ l-B-hydroxyethylamino-Z-nitro-4-( N-methyl- N-B-diethylaminoethyl )amino-benzene 1- dihydrochloride 0.304 g l-B-aminoethylamino- 2-nitro-4-methyl-5- amino'benzene 0.042 g Laurie alcohol oxyethylenated with 10.5 mols of ethylene oxide 2 g Na CO in twice normal solution, q.s.p. pH 7 Water, q.s.p. 100 g This composition is applied to rigorously bleached hair and left for 10 minutes followed by rinsing and shampooing. The result is a deep copper mahogany.

EXAMPLE 30 The following tinctorial composition is prepared:

[ l-N-methylamino-2-nitro-4-( N-waminobutyl )-amino benzene dihydrochloride 0.233 g l-B-aminoethylamino-2-nitro-4-methyl-5 amino benzene 0.052 g Laurie alcohol oxyethylenated with 10.5 mols of ethylene oxide 2 g Na,CO; in twice normal solution, q.s.p. pH 9 Water, q.s.p. 100 g This composition is applied to natural 100% white hair and left for 10 minutes, followed by rinsing and shampooing. The result is a deep pearly blond.

EXAMPLE 31 The following tinctorial composition is prepared:

[ 1-N43-aminoethylamino-2-nitro-4-amino- This composition is applied to natural 100% white hair and left for 10 minutes, followed by rinsing and shampooing. The result is a deep red with purple overtones.

EXAMPLE 32 The following tinctorial composition is prepared:

[ l-N-methylamino-2-nitro-4-waminohexylamino-benzene]-dihydrochloride 1.5 g Lauric alcohol oxyethylenated with 10.5 mols of ethylene oxide 5.0 g Na CO in twice normal solution, q.s.p. pH 8 Water. q.s.p. 100 g This composition is applied to natural 100% white hair and left for 10 minutes, followed by rinsing and shampooing. The result is a very strong violet shade.

EXAMPLE 33 The following tinctorial solution is prepared:

[ lN-methylamino-2-nitro-4-N' y-(methyl-fihydroxyethyl )-arninopropylamino-benzene dihydrochloride 0.50 g Laurie alcohol oxyethylenated with 10.5 mols of ethylene oxide 5.00 g Na CO in twice normal solution. q.s.p. pH 9 Water, q.s.p. 100 g This composition is applied to light chestnut hair and left for 20 minutes, followed by rinsing and shampooing. The result is a deep violine hue.

EXAMPLE 34 The following tinctorial composition is prepared:

Dihydrochloride of l-N-B-diethylaminoethylamino-2-nitro-4-N"di-B- hydroxyethylaminwbenzene 0.41 3 Laurie alcohol oxyethylenated with 10.5 mols of ethylene oxide 5 g Na CO in twice normal solution. q.s.p. pH 7 Water, q.s.p. 100 g This composition is applied to deep golden blond hair and left for 10 minutes, followed by rinsing and shampooing. The result is a chestnut with pearly glints.

EXAMPLE 35 The following tinctorial composition is prepared:

Dihydrochloride of l-N-B-(diethylamino)- ethylamino-2-nitro-4-N'-di-fi- This composition is applied to 90% white hair and left for 10 minutes, followed by rinsing and shampooing. The result is a light golden blond.

EXAMPLE 36 The following tinctorial composition is prepared:

l-N--y-( diethylamino)-propylamhio-2-nitro-4- N-di-B-hydroxyethylamino benzene dihydrochloride 0.43 g Lauric alcohol oxyethylenated with 10.5 mols of ethylene oxide 1.5 g 2 N solution of Na CO q.s.p. pH 9 Water, q.s.p. 100 g This solution is applied to white hair. It is left for 15 minutes. The hair is then rinsed and shampooed. A strong violet gray results.

EXAMPLE 37 the following tinctorial composition is prepared:

4-nitro-3-B-aminoethylamino-N,N-dimethylaniline 0.02 g l-N-- diethylamino)-propylamino-2-nitro-4- N'-di-fi-hydroxyethylamino benzene dihydrochloride 0.38 g Lauric alcohol oxyethylenated with 10.5 mols of ethylene oxide 1 g 2 N solution of Na,CO,. q.s.p. pH 8.5 Water. q.s.p. g

This composition is applied to 90% white hair. It is left to act for 10 minutes. The hair is then rinsed and shampooed. An ash blond shade results.

It will of course be appreciated that the foregoing examples have been given purely by way of illustration and may be modified as to detail without thereby departing from the basic principles of the invention.

All of the compounds of this invention may be made by reacting substituted amino chloride or halide with an alkaline, such as Na, K, etc. or alkaline earth such as Ca, Mg, etc. metal salt of an aromatic or phenyl N-aryl or phenyl sulfonyl amine in the manner illustrated by Example 2.

Other illustrative compounds of this invention which can be converted to the corresponding nitro diamino benzene dye compounds are:

COCH;

HOHQC l NHCuHu What is claimed is: 1. A compound selected from the group consisting of a compound having the formula:

COOH; (Ill) in which R and R, are selected from the group consisting of hydrogen, lower alkyl and lower hydroxyalkyl, R is selected from the group consisting of hydrogen, lower alkyl and lower hydroxyalkyl, R is selected from the group consisting of hydrogen and methyl, and n is an integer between 2 an 6 inclusive, and a compound having the formula:

fin-Q41.

urea: 

2. A compound of claim 1, in which said compound has the Formula III.
 3. A compound of claim 2, in which R1, R2 , R3 and R4 are H.
 4. A compound of claim 1, in which said compound has the Formula IV.
 5. A compound of claim 4, in which R1, R2 and R4 are H. 